EP0666267B1

EP0666267B1 - Organometallic fluorenyl compounds, preparation, and use

Info

Publication number: EP0666267B1
Application number: EP94119735A
Authority: EP
Inventors: Helmut G. Alt; Syriac J. Palackal; Roland Lab. für Anorganische Chemie Zenk; M. Bruce Welch; Michael Lab. für Anorganische Chemie Schmid
Original assignee: Phillips Petroleum Co
Current assignee: Phillips Petroleum Co
Priority date: 1994-02-03
Filing date: 1994-12-14
Publication date: 2001-04-18
Anticipated expiration: 2014-12-14
Also published as: NO944857D0; NO944857L; CN1109472A; EP0666267A2; EP0666267A3; AU1028495A; US5571880A; DE69427117T2; CA2135225A1; CN1060176C; JPH07278169A; RU94043773A; CA2135225C; DE69427117D1; ES2155841T3; AU667449B2

Description

This application is related to the subjects of EP-A-0 524 624, EP-A-0 512 554 and EP-A-0 628 577.
This invention relates to organometallic compounds. More specifically, this invention relates to organometallic compounds containing at least one fluorenyl ligand. In another aspect, this invention relates to polymerization catalyst systems which contain organometallic fluorenyl compounds. In still another aspect, this invention relates to a method for polymerizing olefins using such organometallic fluorenyl compounds and to the polymers resulting from such polymerizations.

Background of the Invention

Since the discovery of ferrocene in 1951, a number of metallocenes have been prepared by the combination of compounds having cyclopentadienyl structure with various transition metals. The term "cyclopentadienyl structure" as used herein refers to the following structure.
The term "cyclopentadiene-type compounds as used herein refers to compounds containing the cyclopentadiene structure. Examples include unsubstituted cyclopentadiene, unsubstituted indene, unsubstituted fluorene, and substituted varieties of such compounds. Also included is tetrahydro indene. Thus polycyclic cyclopentadiene compounds are included within the term.
Many of the cyclopentadiene-type metallocenes have been found useful in catalyst systems for the polymerization of olefins. It has been noted in the art that variations in the chemical structure of such cyclopentadienyl-type metallocenes can have significant effects upon the suitability of the metallocene as a polymerization catalyst. For example, the size and substitutions on cyclopentadienyl-type ligands has been found to affect the activity of the catalyst, the stereoselectivity of the catalyst, the stability of the catalyst, and other properties of the resulting polymer; however, the effects of various substituents is still largely an empirical matter, that is, experiments must be conducted in order to determine just what effect a particular variation will have upon a particular type of cyclopentadienyl-type metallocene. Some examples of some cyclopentadienyl-type metallocenes are disclosed in U.S. Patent Nos. 4,530,914; 4,808,561; and 4,892,851.
While there are references in the prior art which have envisioned metallocenes containing fluorenyl groups, only a very limited number of fluorenyl-containing metallocenes have actually been prepared prior to the present invention. The Journal of Organometallic Chemistry, Vol. 113, pages 331-339 (1976) discloses preparing bis-fluorenyl zirconium dichloride and bis-fluorenyl zirconium dimethyl. U.S. Patent 4,892,851 and the New Journal of Chemistry, Vol. 14, pages 499-503, dated 1990, each disclose preparing a metallocene from the ligand 1-(cyclopentadienyl)-1-(fluorenyl)-1, 1-dimethylmethylene. The New Journal of Chemistry article also discloses preparing a similar compound in which the cyclopentadienyl radical has a methyl substituent in the 3-position. The term fluorenyl as used herein refers to 9-fluorenyl unless indicated otherwise.
EP 0 577 581 A2 relates to a method for controlling the melting point and the molecular weight of syndiotactic polyolefins using metallocene catalyst systems. Several types of metallocene catalyst systems using bridged fluorenyl, fluorenyl-indenyl or fluorenyl-cyclopentadienyl ligands are disclosed.
EP 0 574 370 A1 relates to a syndio specific metallocene of a substituted iPr ((cyclopentadienly) (fluorenyl)) zirconium dichloride containing a long chain alkene, for example octenyl groups on fluorenyl at C2/C7.
EP 0 528 287 A1 discloses bridged metallocenes, how to produce said metallocenes and their use as a catalyst.
EP 0 498 675 A3 is also related to a metallocene catalyst for olefin polymerization. Said catalyst is a substituted and bridged dicyclopentadienyl transition metallocene compound, wherein the transition metal selected from the group of IV B-VI B elements of the periodic table.
The performance of the above catalyst and the properties of the polyolefins obtained therewith is still not satisfying and must thus be improved.
An object of the present invention is to provide certain new fluorenyl-containing metallocenes. Another object of the present invention is to provide a method for preparing said new fluorenyl-type metallocenes. Stiil another object of the present invention is to provide polymerization catalysts employing said nero fluorenyl-type metallocenes. Still yet another object of the present invention is to provide processes for the polymerization of olefins using fluorenyl-type metallocene catalyst systems.

Summary of the Invention

In accordance with the present invention, there are provided new metallocenes of the formula R" (FlR_n)(CpR_m)MeQ_k, wherein FlR_n is a symmetrically substituted fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydro indenyl, or fluorenyl radical, both FlR_n and CpR_m are different, each R is the same or different and is an organo radical having 1 to 20 carbon atoms, R" is a C₁ to C₂₀ hydrocarbyl structural bridge linking (FlR_n) and (CpR_m). Me is a metal from group IVB, of the Periodic Table, each Q is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms or a halogen, k is a number sufficient to fill out the remaining valences of Me, n is 2 or 4, m is a number in the range of 0 to 7, and wherein the R_n of the symmetrically substituted fluorenyl radical are cycloalkyl, cycloalkenyl, aralkyl, or aromatic radicals.
Particularly preferred compounds are those in which is 2, Cp is a cyclopentadienyl or an indenyl radical and m = 0.
In accordance with another aspect of the present invention, there is provided a method for forming the fluorenyl-containing metallocenes described above, the method comprising the step of reacting an alkali metal salt of the selected fluorenyl compound with a transition metal compound of the formula MeQ_k+1 in the presence of a non-halogenated solvent for the fluorenyl salt, which solvent is non-coordinating with respect to the transition metal compound.
In accordance with still another aspect of the present invention, there is provided a process for the polymerization of olefins comprising the step of contacting said olefins under suitable reaction conditions with a catalyst system comprising a fluorenyl-containing metallocene as described above in combination with suitable organoaluminum co-catalyst.

Detailed Description of the Invention

The novel metallocenes provided in accordance with the present invention are bridged metallocenes. Methods for preparing fluorenyl-containing cyclopentadiene-type compounds which can be used in making the metallocenes are disclosed in the aforementioned EP-A-0 512 554.
Me is a metal of the group IVB, metals of the Periodic Table. They include titanium, zirconium, and a hafnium. R" can be any suitable bridging structure. Typical examples include hydrocarbyl and heteroatom-containing alkylene radicals containing 1 to 20 carbon atoms, especially 2 to 20 carbon atoms; germanium: silicon; phosphorus; boron; aluminum; tin; oxygen; nitrogen; and the like. The bridge can even be a cyclic hydrocarbyl structure. Some examples include cyclopentylidene, adamantylidene, cyclohexenylidene, cyclohexylidene, indenylidene, and the like. The R" bridge can be aromatic in nature, such as a phenyl-substituted alkylene; however, the currently preferred modes employ aliphatic alkylene bridges. The currently most preferred bridges are hydrocarbyl or heteroatom-containing alkylene radicals having 1 to 6 carbon atoms. In an especially preferred embodiment k is equal to the valence of Me minus 2.
R can be selected from a wide range of substituents. In the preferred embodiments the substituents R are each independently selected from hydrocarbyl radicals having 1 to 20 carbon atoms. In a particularly preferred embodiment, the hydrocarbyl radicals R are alkyl. aryl, or arylalkyl radicals. More preferably, the alkyl R radicals have 1 to 5 carbon atoms.
Each Q is a hydrocarbyl 1 radical such as, for example, aryl. alkyl, alkenyl, alkaryl, or arylalkyl having from 1 to 20 carbon atoms, or halogen. Exemplary Q hydrocarbyl radicals include methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl, and the like. Exemplary halogen atoms include chlorine, bromine, fluorine, and iodine, and of these halogen atoms, chlorine is currently preferred.
Illustrative examples of inventive metallocenes include 1-(2,7-dimesityl fluorenyl)-1-(cyclopentadienyl)-1, 1-dimethyl methane) zirconium dichloride, 1-(2,7-diphenyl fluorenyl)-1-(cyclopentadienyl)-1-phenyl methane) zirconium dichloride, 1-(2,7-dimesityl fluorenyl)-1-(cyclopentadienyl)cyclopentane) zirconium dichloride, 1-(2-7-diphenylfluorenyl)-1-(cyclopentadienyl) indanylidene zirconium dichloride, and 1-(2,7 bis(dimethyl phenyl carbyl) fluorenyl)-1-(cyclopentadienyl) diphenylmethane zirconium dichloride. In further preferred metallocene species FlR_n is a 1,8- 2,7- 4,5- or 3,6-disubstituted radical.
Particularly preferred metallocene species include wherein Fl, R, R", and m are as defined above, and where n is 2.
According to the instant invention are provided metallocenes containing at least one symmetrically substituted fluorenyl radical. The term symmetrically substituted as used herein refers to fluorenyl radicals having substituents on opposite portions of the fluorenyl radical, such as for example 2,7-dialkylfluorenyl; 2,7-dicycloalkenylfluorenyl; 3,6-dialkylfluorenyl; 2,7-dihalo fluorenyl; 2,7-diarylfluorenyl; 1,8-dialkylfluorenyl; 4,5-dialkylfluorenyl; 2,7-diarylalkylfluorenyl; and the like. Only the substituents listed in claim 1, i.e., cycloalkyl, cycloalkenyl, aralkyl, and aromatic susbtitutents, are covered by the present invention. Preferred substituents are the phenyl radicals. Most preferably, the substituents on the fluorenyl are the same. Examples of aryl substituents include those having 6 to 20 carbon atoms, with those having 6 to 10 carbon atoms being generally more preferred. Likewise, the arylalkyl substituents can contain 7 to 20 carbon atoms, more commonly 7 to 10 carbon atoms. It should be recognized that in certain instances, if the bridge and the substituents on the fluorenyl are particularly bulky it may be difficult to prepare the ligand, the dialkyl salt, or the metallocene.
The inventive metallocenes as well as related metallocenes can be prepared by reacting an alkali metal salt of the bridged fluorenyl compounds with a suitable transition metal compound in a suitable solvent under suitable reaction conditions.
Techniques for preparing the bridged ligands are disclosed in EP-A-0 512 554 and the aforementioned U.S. Patent application Serial No. 08/064,630 and 07/984,054. Methylene-bridged ligands can be made by using 6-or 6,6-substituted fulvenes. Examples of fulvene reactions are disclosed in U.S. Patent No. 4,892,851 and in J. Organomet. Chem. 435, 299-310 (1992). In general, the technique involves reacting an alkali metal salt of the 2,7-substituted fluorene with the selected fulvene type compound. The 6,6-diphenyl fulvenes can be prepared by reacting a suitable aryl bromide, i.e. phenyl bromide, p-tolyl bromide, p-fluorophenyl bromide, or p-t-butylpheny] bromide, with magnesium to form a Grignard reagent, which is hydrolyzed after the dropwise addition of methyl formate to result in the formation of the corresponding diarylcarbinol. The diarylcarbinol can then be oxidized smoothly to give the corresponding substituted benzophenone, preferably using sulfuric acid and chromic acid. The resulting substituted benzophenone can then be reacted with cyclopentadiene in ethanol containing sodium to yield the 6,6-substituted fulvene.
A variation of this technique involves the production of indanyl fulvene (which can also be called indanylidene fulvene) by reacting 1-indanone with cyclopentadiene in the presence of ethanol and sodium ethoxide. The indanyl fulvene is particularly useful in that it can be reacted with the alkali metal salt of a fluorene compound to yield an indanyl bridged fluorenyl cyclopentadienyl compound. An example would be 1-(2,7-diphenylfluorenyl)-1-(cyclopentadienyl) indanylidene.
The symmetrically substituted fluorenyl compounds needed to make the bridged ligands can be prepared using procedures generally known in the prior art. Some particularly desirable techniques for forming certain of the substituted fluorenyl compounds will be described in further detail in what follows.
The term transition metal compound as used herein includes compounds of the formula MeQ_k+2, wherein Me, Q, and k are as defined above. Some non-limiting examples include zirconium tetrachloride, hafnium tetrachloride, titanium tetrachloride, cyclopentadienyl zirconium trichloride, fluorenyl cyclopentadienyl zirconium dichloride, 3-methylcyclopentadienyl zirconium trichloride, indenyl cyclopentadienyl zirconium dichloride, 4-methyl fluorenyl zirconium trichloride, and the like.
Metallocenes in which Q is other than a halogen can be readily prepared by reacting the halide form of the metallocene with an alkali metal salt of the hydrocarbyl radical under conditions as have been used in the past for forming such ligands in prior art metallocenes. See, for example, the aforementioned J. Org. Chem. 113, 331-339 (1976). Another approach involves reacting a compound of the formula MeQ_k+2, wherein at least one Q is hydrocarbyl or hydrocarbyloxy, with the alkali metal salt of the bridged fluorenyl compound.
One embodiment of the present invention involves carrying out the reaction of the fluorenyl-containing salt and the transition metal compound in the presence of a liquid diluent which is non-halogenated and non-coordinating toward the transition metal compound. Examples of such suitable liquid include hydrocarbons such as toluene, pentane, or hexane as well as non-cyclic ether compounds such as diethylether. It has been found that the use of such non-halogenated non-coordinating solvents generally allows one to obtain large amounts of substantially pure metallocenes and in a more stable form; and also often allows the reaction to be conducted under higher temperature conditions, than when THF is used as the diluent. In an especially preferred embodiment the fluorenyl-containing salt used as a ligand is also prepared in a liquid diluent that is non-halogenated and non-coordinating toward the transition metal.
The formation of the alkali metal salt of the fluorenyl compound can be formed using generally any technique known in the art. For example, such can be prepared by reacting an alkali metal alkyl with the cyclopentadienyl type compounds or the bridged compounds having two cyclopentadienyl-type radicals per molecule. The molar ratio of the alkali metal alkyl to the cyclopentadienyl type radicals present can vary, generally however, the ratio would be in the range of 0.5/1 to 1.5/1, more preferably about 1/1. Typically, the alkali metal of the alkali metal alkyl would be selected from sodium, potassium, and lithium, and the alkyl group would have 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Preferably, if the fluorenyl salt is formed using tetrahydrofuran (THF) as the liquid solvent, the salt is isolated and substantially all of the THF is removed before the salt is contacted with the transition metal halide. The molar ratio of the fluorenyl compound to the transition metal compound can vary over a wide range depending upon the results desired. Typically, however, the molar ratio of the bridged fluorenyl compound to the transition metal compound is about 1 to 1.
The resulting metallocene can be recovered and purified using conventional techniques known in the art such as filtration, extraction, crystallization, and re-crystallization. It is generally desirable to recover the metallocene in a form that is free of any substantial amount of by-product impurities. Accordingly, recrystallization and fractional crystallization to obtain relatively pure metallocens are desirable. Dichloromethane has been found to be particularly useful for such recrystallizations. As a general rule, it has been found that the metallocenes based on unbridged fluorenyl compounds are less stable than the metallocene compounds formed from bridged fluorenyl compounds. Since the stability of the various metallocenes varies, it is generally desirable to use the metallocenes soon after their preparation or at least to store the metallocene under conditions favoring their stability. For example, the metallocenes can generally be stored at low temperature, i.e., below 0°C in the absence of oxygen and water.
The resulting fluorenyl-containing metallocenes can be used in combination with a suitable co-catalyst for the polymerization of olefinic monomers. In such processes the metallocene or the co-catalyst can be employed on a solid insoluble particulate support.
Examples of suitable co-catalysts include generally any of those organometallic co-catalysts which have in the past been employed in conjunction with transition metal containing olefin polymerization catalysts. Some typical examples include organometallic compounds of metals of Groups IA, IIA, and IIIB of the Periodic Table. Examples of such compounds have included organometallic halide compounds, organometallic hydrides, and even metal hydrides. Some specific examples include triethyl aluminum, tri-isobutyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, and the like. Other examples of known cocatalysts include the use of a stable non-coordinating counteranion technique such as disclosed in U.S. Patent 5,155,080, e.g. using triphenyl carbenium tetrakis (pentafluorophenyl) boronate. Another example would be the use a a mixture of trimethylaluminum and dimethylfluoroaluminum such as disclosed by Zambelli et al., Macromolecules, 22, 2186 (1989). In such processes, the metallocene or the co-catalyst can be employed on a solid insoluble support.
The currently most preferred co-catalyst is an aluminoxane. Such compounds include these compounds having repeating units of the formula
where R is an alkyl group generally having 1 to 5 carbon atoms. Aluminoxanes, also sometimes referred to as poly(hydrocarbyl aluminum oxides), are well known in the art and are generally prepared by reacting an organo hydrocarbylaluminum compound with water. Such preparation techniques are disclosed in U.S. 3,242,099 and 4,808,561. The currently preferred co-catalysts are prepared either from trimethylaluminum or triethylaluminum, sometimes referred to as poly(methyl aluminum oxide) and poly(ethyl aluminum oxide), respectively. It is also within the scope of the invention to use an aluminoxane in combination with a trialkylaluminum, such as disclosed in U.S. Patent No. 4,794,096.
The fluorenyl-containing metallocenes in combination with the aluminoxane co-catalyst can be used to polymerize olefins. Generally, such polymerizations would be carried out in a homogeneous system in which the catalyst and co-catalyst were soluble; however, it is within the scope of the present invention to carry out the polymerizations in the presence of supported forms of the catalyst and/or co-catalyst in a slurry or gas phase polymerization. It is within the scope of the invention to use a mixture of two or more fluorenyl-containing metallocenes or a mixture of an inventive fluorenyl-containing metallocene with one or more other cyclopentadienyl-type metallocenes.
The fluorenyl-containing metallocenes when used with aluminoxane are particularly useful for the polymerization of mono-unsaturated aliphatic alpha-olefins having 2 to 10 carbon atoms. Examples of such olefins include ethylene, propylene, butene-1, pentene-1,3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-ethylbutene-1, heptene-1, octene-1, decene-1, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3-4-dimethyl-1-hexene, and the like, and mixtures thereof. The catalysts are particularly useful for preparing copolymers of ethylene or propylene and generally a minor amount, i.e., less than 20 mole percent, more commonly about 12 mole percent, more typically less than 10 mole percent, of the higher molecular weight olefin.
The polymerizations can be carried out under a wide range of conditions depending upon the particular metallocene employed, and the results desired. Examples of typical conditions, under which the metallocenes can be used in the polymerization of olefins include conditions such as disclosed in U.S. Patents 3,242,099; 4,892,851; and 4,530,914. It is considered that generally any of the polymerization procedures used in the prior art with any transition metal-based catalyst system can be employed with the present fluorenyl-containing metallocenes.
Generally the molar ratio of the aluminum in the aluminoxane to the transition metal in the metallocene would be in the range of 0.1:1 to 10⁵ : 1 and preferably 5:1 to 10⁴ : 1. As a general rule, the polymerizations would be carried out in the presence of liquid diluents which do not have on adverse affect upon the catalyst system. Examples of such liquid diluents include propane, butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, and the like. The polymerization temperature can vary over a wide range, temperatures typically would be in the range of -60°C to 280°C, preferably in the range of 20°C to 160°C. Typically, the pressure would be in the range of 100 kPa to 50 MPa, corresponding to approximately 1 to 500 atmospheres, or greater.
The polymers produced with this invention have a wide range of uses that will be apparent to those skilled in the art from the physical properties of the respective polymer. Some of the catalysts are useful for preparing syndiotactic polymers. The term syndiotatic polymer as used herein is intended to include those polymers having segments of more than 10 monomeric repeating units in which the alkyl group of each successive monomeric unit is on the opposite side of the plane of the polymer.

Preparation of symmetrical di-substituted fluorenyl compounds

As noted previously, there are various procedures known in the art for preparing many symmetrical di-substituted fluorenyl compounds. The production of 2,7-dichlorofluorene can be carried out as disclosed by A. Roedig, Houben/Weyl 5/4 330-41, i.e, by contacting fluorene with chlorine in the presence of N-chlorosuccimide. 2,7-dibromofluorene can be obtained by bromination of fluorene in CHCl₃ or CH₂Cl₂ at 0°C using procedures generally as taught in J. Am. Chem. Soc., 84, 1238-41 (1962); Bull. Chem. Soc. Jp, 44, 1614-19 (1971); or J. Chem. Soc., 43, 164-5 (1883). 2,7-diiodofluorene can be obtained using the procedure described in Helv. Chem. Acta, 53, 1311-23 (1970). The diiodofluorene car be separated from monoiodofluorene by crystallization from hot THF or toluene. 2,7-di-t-butylfluorene can be obtained using procedures of the type shown in Synthesis, 335-7 (1984) and Bull. Chem. Soc. Jp., 59, 97-103 (1986).
Multistep procedures are known in the art for producing 2,7-dimethoxyfluorene. It has been surprisingly discovered that the compound can be produced in one step using the copper-catalyzed methanolysis of 2,7-dibromofluorene using conditions similar to those disclosed in Tetrahedron Letters, 34, 1007-1010 (1993) involving the use of ethyl acetate and concentrated sodium methoxide solutions.
2,7-bis(dimethylphenylcarbyl) fluorene, which is believed to be a new compound, was prepared by reacting benzoic acid with fluorene in hot polyphosphoric acid at about 100°C to yield 2,7-dibenzoylfluorene which is then reacted with trimethyl aluminum in boiling toluene.
2,7-di(1-cyclohex-1-enyl)fluorene can be prepared by first forming a Grignard reagent from 2,7-diiodofluorene and magnesium and bromoethane in THF by heating for several days in a Schlenk tube at 60-90°C. Then cyclohexanone is added. After acidic workup in hot toluene, the 2,7-dicyclohexenyl fluorene is obtained.
A new shorter preparation of 2,7-substituted alkyl and aryl fluorenes is a further invention. The examples of substituents include cycloalkyl such as cyclohexyl; phenyl, and even sterically strained mesityl or naphthyl moieties. The process involves reacting 2,7-diiodofluorene in diethyl ether with the appropriate Grignard reagent. Generally, it is desirable to use nickel phosphine, i.e. Ni(tpp)₂Cl₂, as a catalyst for the crossed coupling reaction. Literature references disclosing similar uses of the nickel phosphine are disclosed in Pure Appl. Chem., 52; 669-75 (1980); J. Chem. Soc., 1490-4 (1962); and Inorg. Chem., 5, 1968-74 (1966). The liquid diluent for the reaction can vary over a wide range depending upon the results desired. Typical liquid diluents include tetrahydrofuran, diethylether, toluenes, and the like. Isolation is generally made by acidic hydrolysis and extraction with boiling toluene.
Examples of 2,7-substituted fluorenes that can be produced include 2,7-dicyclohexylfluorene; 2,7-dimethylfluorene; 2,7-diisopropylfluorene; 2,7-diphenylfluorene; 2,7-di(1-naphthyl) fluorene; 2,7-di(4-methvlphenyl) fluorene; 2,7-di(2,4-dimethylphenyl) fluorene; 2,7-di(mesityl)fluorene, 2,7-di(4-fluorophenyl) fluorene; and the like.
Other routes are available for producing 2,7-substituted fluorene compounds. The compound 2,7-diacetylfluorene can he obtained by the acetylation of fluorene with acetic anhydride and aluminum trichloride. In the prior art such reactions have been conducted in 1,2-dichloroethane. It has now been discovered that even higher yields can be obtained by using the safer solvent methylene chloride. A hydrogen reduction of the diacetylfluorene with Pd on carbon results in 2,7-diethylfluorene. On the other hand, the reaction of the diacetyl with trimethyl aluminum results in 2,7-di-t-butylfluorene. This new technique is superior to the prior art technique involving t-butylation of fluorene with butyl cresol in that it is more selective to the 2,7-isomer.
Similarly, 2,7-bis(dimethylphenylcarbyl) fluorene can be obtained by stirring fluorene and benzoic acid in polyphosphoric acid at about 100°C to obtain 2,7-dibenzoylfluorene which is then reacted with trimethylaluminum to yield the 2.7-bis(dimethylphenylcarbyl) fluorene.
An improved shortened process for preparing 4,5-dimethylfluorene involves reacting fuming nitric acid with m-toluic acid to form 3-methyl-2-nitrobenzoic acid which is reduced to 2-amino-3-methyl benzoic acid. Preferably, the reduction is carried out using hydrogen and a Pd on carbon catalyst. Diazotization and coupling of that product results in 6,6'-dimethyldiphenic acid which can then be cyclized using polyphosphoric acid to form 4,5-dimethylfluorenone, which in turn can be hydrogenated over palladium on carbon to form 4,5-dimethylfluorene.
3,6-di-t-butylfluorene can be prepared with greater selectivity than prior art methods by brominating 4-t-butyl toluene and reacting that product with magnesium in THF using a Ni(tpp)₂Cl₂ catalyst. A preferred method for carrying out the bromination involves using an excess of N-bromosuccimide in CCl₄ together with subsequent hydrolysis of the crude product with CaCO₃ in water/dioxane. The coupled substituted biphenyl product is then subjected to oxidation with KMnO₄ in aqueous acetone. Ring closure is then effected by using hot polyphosphoric acid. The undesired by-products are separated by extraction using an ether/aqueous carbonate solution. The recovered 3,6-di-t-butylfluorenone is then hydrogenated using a palladium on carbon catalyst.
A further understanding of the present invention, its various aspects, objects and advantages will be provided by the following examples.
In the following examples, where information is given about the microstructure of polymers as determined by ¹³CNMR, the spectra were taken using standard accepted spectroscopy techniques. The polymer was dissolved in trichlorobenzene and the spectra were taken with respect to an internal standard relative to hexamethylsiloxane which has a known reference point relative to tetramethyl silane. From the observed integrals of the relevant peaks, the details regarding the microstructure are calculated. Meso Content = (mm) + 1/2 (mr) Racemic Content = (rr) + 1/2 (mr) Isotacticity = % (mm) Heterotacticity = % (mr) Syndiotacticity = % (rr) Randomness Index = (mr)1002(m)(r) Average Tsotactic Block Length = 1 + 2(mm)(mr) Average Syndiotactic Block Length = 1 + 2(rr)(mr) For more details regarding the determination of these values, reference is made to Chapter 3 of the aforementioned book by Frank A. Bovey.

Examples

Example I

Preparation of 1-bromo-2-(fluorenyl)ethane

In this reaction, 8.3 g (0.05 m) fluorene was dissolved in 150 ml tetrahydrofuran. Then 31.8 ml (0.05 m) butyl lithium (1.6 molar in hexane) was added dropwise to this solution. After one hour, this solution was added gradually to a stirred solution of 9 ml (0.1 m) dibromoethane in 300 ml of pentane within 2 hours. Then the reaction mixture was treated with 50 ml of an aqueous NH₄Cl solution, and then washed with 50 ml of water. The organic phase was dried over Na₂SO₄. Then the solvent was removed in vacuo. The yellow residue was dissolved in pentane. The pentane solution was filtered over silica. The solution was concentrated to about 20% of the original volume, and then the product was crystallized at -30°C. A yield of 10.88 g 1-bromo- 2-(fluorenyl)ethane was obtained. The product was characterized through ¹H-NMR, ¹³C-NMR, and Mass spectroscopy.

Example II

Reactions similar to that set forth in Example I have been carried out substituting other dihalo alkylenes for 1,2-dibromo ethane. Examples include 1,3-dibromopropane, 1,2-di-bromomethane, 1,2-dibromo-2-methyl ethane, and dichloromethane. The corresponding fluorenyl alkyl halides were obtained.

Example III

Cyclopentadiene was reacted with butyl lithium in tetrahydorofuran to yield cyclopentadienyl lithium. A solution of 0.002 mole cyclopontadienyl lithium in 150 ml tetrahydrofuran at (-40 degrees C) and a solution of 1-bromo-2-(fluorenyl) ethane in 50 ml THF were mixed togeter at room temperature. Then 10 ml hexamethyl phosphine triamide (HMPT) were added. After three hours stirring at room temperature, this solution was washed with 50 ml aqueous NH4Cl solution, then washed with 50 ml of water, and then the organic phase was dried over Na2SO4. The solvent was removed in vacuo. The resulting 1-(fluorenyl)-2-cyclopentadienyl ethane can be purified by dissolving in pentane and then cyrstallizing. The product was characterized by mass spectroscopy and gas chromatography.

Example IV

Reactions similar to that set forth in Example III were carried out substituting other fluorenyl bromo alkanes for the fluorenyl promo ethanes. Examples of the other bromo alkanes used included 1-fluorenyl-3-bromo propane, 1-(2,7-di-tert-butyl fluorenyl)-1-bromo methane, and 1-methyl-2-fluorenyl-1-bromo ethane. The corresponding alkyl-bridged fluorenyl-cyclopentadienyl compounds were obtained. Also using a reaction similar to that of Example III but without the HMPT 2,7,-di-tert-butyl fluorene was substituted for cyclopentadiene. The product 1-(2,7-di-tert-butyl fluorenyl)-2-fluorenyl ethane was recovered.

Example V

A number of fluorenyl-containing metallocenes were prepared using either diethyl ether or toluene as a solvent.
When diethyl ether was used as a solvent, about 1 millimole of the respective fluorenyl compound was dissolved in 200 ml ether. Then 1.6 molar methyllithium in diethyl ether was added to the solution to provide 1 millimole of methyllithium for each millimole of cyclopentadienyl-type radical. (An exception would be in the case in which it was desired to produce a mono-valent salt of the bridged fluorenyl compound. In such a case only about 0.5 millimole of methyllithium would be used for each millimole of cyclopentadienyl-type radicals.) The reaction mixture was stirred until no additional methane gas was evolved. This was done at room temperature. Next, the transition meta' halide was added in small portions to the solution of the fluorenyl salt. The amount of transition metal was about 0.5 millimole, when the fluorenyl compound was a monovalent salt, and about 1 millimole when the fluorenyl compound was a divalent salt. The resulting solution was typically stirred for additional 30 minutes and then concentrated to about 50 ml and filtered. The orange-to red-colored solids remaining on the filter plate were dissolved in dichloromethane, and the resulting solution was concentrated and recrystallized, generally at about -78°C.
In the runs prepared using toluene as the solvent, about 1 millimole of the fluorenyl compound was mixed with 250ml toluene. This mixture was combined with methyllithium (1.6 molar in diethyl ether) in an amount sufficient to provide 2 millimoles of the methyllithium. (Again the exception discussed in the previous paragraph also applies.) Then the reaction mixture was heated at reflux until no more methane gas was being released. The solution was then allowed to cool to room temperature. The transition metal halide was then slowly added to the solution. Again, about 0.5 millimoles of transition metal compound was employed with the divalent fluorenyl salts and about 1 millimole was employed with the monovalent fluorenyl salts. The suspension was then stirred for about 30 minutes. The solution was then concentrated to 50 to 75 ml and filtered. The orange to red solids on the filter plate were dissolved in dichloromethane, and the resulting solution was concentrated and cooled to -78°C to obtain the metallocene as a solid precipitate.
Procedures of those general types have been used to prepare the following metallocenes:
(1,2-difluorenyl ethane) zirconium dichloride; (1-fluorenyl-2-indenyl ethane) zirconium dichloride and hafnium dichloride; (1-fluorenyl-1-cyclopentadienyl methane)zirconium dichloride; (1-fluorenyl-1-cyclopentadienyl methane)zirconium trichloride, (1,2-di(2-tert butyl fluorenyl) ethane) zirconium dichloride and hafnium dichloride; (1,2-di(2-methyl fluorenyl)ethane) zirconium dichloride; (1,2-difluorenyl ethane) hafnium dichloride; bis (2,7-tert butyl-4-methyl fluorenyl)zirconium dichloride; (1,3-difluorenyl propane) zirconium dichloride and hafnium dichloride; (1-fluorenyl-2-methyl-2-fluorenyl ethane) zirconium dichloride; dimethyl silyl difluorenyl zirconium dichloride; (1,2-di(1-methyl fluorenyl)ethane) zirconium dichloride; (1,2-di(1-tert butyl fluorenyl)ethane) zirconium dichloride and hafnium dichloride: (1,2-di(2-ethyl fluorenyl)ethane) zirconium and hafnium dichloride; (1,2-di(4-tert butyl fluorenyl)ethane zirconium dichloride; (1-fluorenyl-2-cyclopentadienyl ethane) zirconium dichloride; (1-fluorenyl-2-(3-methylcyclopentadienyl) ethane zirconium dichloride; (1-fluorenyl-3-indenyl propane) zirconium dichloride; (1-fluorenyl-2-methyl-2-cyclopentadienyl ethane) zirconium dichloride; (1-fluorenyl-2-methyl-2-indenyl ethane) zirconium dichloride; (1-fluorenyl-2-methyl-2-(3-methylcyclopentadienyl)ethane) zirconium dichloride; (1-(1-methyl fluorenyl)-2-(4-methyl fluorenyl)ethane) zirconium dichloride; (1-(1-tert butyl fluorenyl)-2-(4-tert butyl fluorenyl) ethane) zirconium dichloride; bis (2,7-di-tert butyl-4-methyl fluorenyl) zirconium dichloride; (1,2-difluorenyl ethane) vandium dichloride. (1,1-difluorenyl methane) vanadium dichloride, bis(1-methyl fluorenyl) zirconium dichloride; bis (1-methyl fluorenyl) hafnium dichloride; bis(2-ethyl fluorenyl)zirconium dichloride; bis (4-methyl fluorenyl) zirconium dichloride, and bis (4-methylfluorenyl) hafnium dichloride.

Use of Fluorenyl Metallocenes

A number of fluorenyl-containing metallocenes prepared in accordance with the present invention was evaluated for their effectiveness as catalysts for the polymerization of olefins. The specific metallocenes evaluated are referred to in the following tables as follows:

Catalyst

A: (1,2-difluorenyl ethane) zirconium dichloride
B: (1-fluorenyl-2-indenyl ethane) zirconium dichloride
C: (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride
D: (1,2-di(2-tertbutyl fluorenyl)ethane) zirconium dichloride
E: bis (2,7-tertbutyl-4-methyl fluorenyl) zirconium dichloride
F: (l-fluorenyl-1-cyclopentadienyl methane) zirconium trichloride
H: (1-fluorenyl-2-methyl-2-indenyl ethane) zirconium dichloride
I: (1,2-difluorenyl ethane) hafnium dichloride

The catalyst system solution was added to the polymerization reactor which had been suitably prepared for the particular polymerization to be conducted. Typically for the polymerization of propylene the reactor contained liquid propylene as the reaction diluent. For polymerizations of ethylene or 4-methyl-1-pentene liquid isobutane diluent was employed. After the catalyst was charged monomer and hydrogen, if employed, were added at room temperature. The reaction was then allowed to proceed for a period of time at which the reactor was cooled in an attempt to maintain a selected reaction temperature. In most cases, after the polymerization was complete the diluent was flashed off and the polymer solids recovered and characterized. In some cases where the polymer was of low molecular weight or substantially all in solution the liquid would be drained and the unreacted monomer, comonomer, and/or diluent removed by evaporation.
Various characteristics of the polymer and the polymerization were characterized. Examples of characteristics determined in various cases include density in g/ml (ASTM D1505-68); Melt Flow Index in g of polymer/10 minutes (ASTM D1238-65T, Condition L); High Load Melt Index in g of polymer/10 minutes 190°C (ASTM D1238, Condition E); Melt Index in g of polymer/10 minutes 190°C (ASTM D1238, Condition E); heptane insolubles determined by the weight percent of insoluble polymer remaining after extraction with boiling heptane; melting point in degrees centigrade by Differential Scanning Calorimetry; molecular weights by size exclusion chromatography, i.e.,weight average molecular weight referred to herein as Mw and number average molecular weight referred to herein as Mn; heterogenity index determined by dividing Mw by Mn. The (SEC) size exclusion chromatography was conducted using a linear column capable of resolving the wide range of molecular weights generally observed in polyolefins, such as polyethylene. The SEC used a 1,2,4-trichlorobenzene solution of the polymer at 140°C. The intrinsic viscosity was calculated from the SEC using the Mark-Houwink-Sakrada constants, i.e., k·MW^a in deciliter/g, referred to in the following tables as IV. Unless indicated otherwise the conditions employed for characterizing the various properties were the same for each polymer evaluated. In some cases, infrared and 13C-NMR spectra were taken of the polymer. The NMR spectra were conducted with a 1,2,4-trichlorobenzene solution of the polymer. The base standard in the NMR spectra was 0 ppm based on tetramethylsilane.

Example VI

Ethylene Polymerization With (1,2 difluorenylethane) zirconium dichloride

A number of polymerization runs were conducted to evaluate the effectiveness of (1,2-difluorenylethane) zirconium dichloride as a catalyst for the polymerization of ethylene both alone and with a comonomer. The various polymerization variables and the results are summarized in the following Table. The value reported for comonomer when used in all the following tables refers to g of the comonomer. Also yields are in g.
The table demonstrates that the fluorenyl-containing metallocene is capable of producing polymers of ethylene having a wide range of properties. In the absence of hydrogen the polymer was a very high molecular weight material as evidenced by the low HLMI, i.e., High Load Melt Index. The data further demonstrates that copolymerization of ethylene and hexene can result in lower density polymers.

Example VII

Ethylene Polymerization with Various Bridged Fluorenyl Metallocenes

A number of ethylene polymerizations were also conducted using other bridged metallocenes. The various polymerization variables and the results are summarized in the following Table. Runs 4 and 5 from the previous Table are included for comparison.
The Table demonstates that (1-fluorenyl-2-indenyl ethane) zirconium dichloride, i.e, Catalyst B, and Catalyst C, i.e, (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride, are also suitable for the polymerization of ethylene. Catalyst C gave a higher molecular weight material as indicated by the HLMI values. Run 14 demonstrates that Catalyst C is also capable of producing a copolymer of ethylene and hexene. The particular copolymer produced in this run is particularly unusual in that it contains 12.4 mole percent comonomer and a relative comonomer dispersity of 105.9. The mole percent comonomer and relative comonomer dispersity were determined from NMR spectroscopy using the technique disclosed in U.S. 4,522,987. Such a polymer can be referred to as a low density super random copolymer, i.e., a polymer having a super random distribution of the comonomer.

Example VIII

Propylene Polymerization With Various Fluorenyl Metallocenes

A number of polymerizations of propylene were conducted using various fluorenyl-containing metallocenes. The reaction variables and the results are summarized in the following Table.
Table III demonstrates that Catalyst C, i.e., (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride, can be used to produce a polymer from propylene. The data in runs 15-17 shows that the polypropylene is highly crystalline as demostrated by the heptane insolubles values. It is believed that the polymer contains high levels of syndiotactic molecular structure.
Run 20 demonstrates that Catalyst D, i.e., (1,2-di(2-tert butyl fluorenyl)ethane) zirconium dichloride, can be used to produce a crystalline polypropylene.
Run 21 demonstrates that Catalyst E, i.e.) the unbridged metallocene bis(2,7-di-tertbutyl-4-methyl fluorenyl) zirconium dichloride, produced onlv a small amount of solid polypropylene at 60°C. Run 22 shows that Catalyst E was not particularly effective at all at 23.4°C.
Run 23 and 24 employed a non-sandwich bonded metallocene, i.e., a metallocene in which only one of the cyclopentadienyl-type radicals was bonded to the transition metal. The catalyst produced only 3 to 5 g of solid polymer along with 45 to 55 g of low molecular weight propylene soluble polymer. Unless indicated otherwise by the formula or other means, all the bridged metallocenes referred to herein are sandwich-bonded.
Run 26 employed (1-fluorenyl -2-indenyl ethane) zirconium dichloride. Although this catalyst yielded 460 g solid polymer, 94.4 weight percent of the polymer was a low molecular weight xylene- soluble polymer. Similarly, (1-fluorenyl-2-methyl-2-indenyl ethane) zirconium dichloride in Run 27 yielded 82 g of a solid, 88 weight percent of which were low molecular weight xylene-soluble material.
Runs 28 and 29 employed bridged metallocenes based on 1,2-difluorenyl ethane. Both the zirconium and the hafnium metallocenes yielded solid polypropylene.

Example IX

Catalyst C, i.e., (1-fluorenyl-l-cyclopentadienyl methane) zirconium dichloride, was evaluated as a catalyst for the polymerization of 4-methyl-1-pentene. The amount of the metallocene employed was 5 mg. The polymerization was conducted in the presence of hydrogen with the differential pressure of the hydrogen being 25. The polymerization temperature was 120°C and the length of the polymerization was 2 hours. The polymerization resulted in the production of 96.7 g of a solid having a weight average molecular weight of 33,330; a heterogenity index of 1.3; and a calculated intrinsic viscosity of 0.12. About 92 weight percent of the solid were insoluble in boiling heptane. The polymer had a melting point of 197.9°C. A 13C-NMR spectrum was taken of the polymer as recovered, i.e., without heptane-solubles removed, and it indicated that the polymer contained a substantial amount of syndiotactic functionality. Significant peaks were observed at about 22.8, 24.8, 26, 31.8, 42.8, 43.1, 46.1, and 46.2 ppm. The intensity of the peak at 43.1 ppm has greater than 0.5 of the total peak intensities in the range of 42.0 and 43.5 ppm. The peak at about 46.2 ppm had a greater intensity than any peak between the major peaks at 46.1 and 43.1 ppm. Further, the peak at about 42.8 ppm had a greater intensity than any peak between the major peaks at 46.1 and 43.1 ppm. These peak locations are relative to a peak of zero ppm for tetramethylsilane.

Example X

Under conditions substantially as used in Example VIII, a run was carried out attempting to polymerize 4-methyl-1-pentene with Catalyst A, i.e., (1,2-difluorenyl ethane) zirconium dichloride. In this case 7 mg of the catalyst were employed and 180 g of solid atactic wax-like polymer were obtained.
A similar run was conducted substituting the unbridged metallocene, bis(2-methylfluorenyl) zirconium dichloride for Catalyst A in the polymerization of 4-methyl-1-pentene.
In this run, 5 mg of the metallocene were used and 9.7 g of solid polymer were recovered. Two samples of the polymer were subjected to heptane extraction. The extraction gave heptane-insoluble values of 54.8 and 68.8. The catalyst was thus not as active as either the Catalyst mentioned in the proceding paragraph or Catalyst A.

Example XI

Polymerizations were carried out to compare the effects of different metallocenes on the polymerization of propylene. The polymerizations were conducted under particle form conditions using propylene as the diluent. The metallocene was used in conjunction with a methylaluminoxane cocatalyst. Polymerizations were conducted both with and without hydrogen. Each polymerization involved weighing a metallocene in a dry box and dissolving it in a 10% solution of methylaluminoxane and toluene obtained from Schering AG. The aluminum to zirconium molar ratio was 1,000/1. The charge order was metallocene/MAO, 15 psi hydrogen as measured as the pressure dropped on a 300 ml cylinder (when used), and two-thirds of a gallon of liquid propylene. After heating these materials to 70°C, the content of the reactor was stirred at that temperature for one hour. The polymerization was then terminated by venting off surplus propylene. The polymer was recovered, dried and weighed to determine the yields. The results are summarized in Table IV.
(2,7-di-phenylfluorenyl)(cyclopentadienyl) dimethylmethane zirconium dichloride of Runs 1 and 2 did result in a higher molecular weight polymer.
(2,7-di-phenylfluorenyl)(cyclopentadienyl) diphenylmethane zirconium dichloride of Runs 3 and 4 produced a remarkably high molecular weight polymer.

Claims

A metallocene of the formula R"(FlR_n)(CpR_m)MeQ_k, wherein FlR_n is a symmetrically substituted fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydro indenyl, or fluorenyl radical, both FlR_n and CpR_m are different, each R is the same or different and is cycloalkyl, cycloalkenyl, aralkyl, or aromatic radical, in particular phenyl, R" is a C₁ to C₂₀ hydrocarbyl structural bridge linking FlR_n and CpR_m, Me is a metal of group IVB of the Periodic Table, each Q is the same or different and is a hydrocarbyl radical having 1 to 20 carbon atoms or a halogen, k is a number sufficient to fill out the remaining valences of Me, n is 2 or 4, and m is a number in the range of 0 to 7.
The metallocene of claim 1, wherein FlR_n is a 1,8-, 2,7-, 4,5-, or 3,6-disubstituted radical.
The metallocene of claim 1 or 2, wherein Me is Zr.
The metallocene of any of the preceding claims, wherein Cp is a cyclopentadienyl or an indenyl radical.
The metallocene of any of the preceding claims, wherein m is 0.
The metallocene of any of the preceding claims, said metallocene being selected from:

(1-(2,7-diphenyl fluorenyl)-1-cyclopentadienyl-1,1-diphenylmethane) zirconium dichloride;

(1-(2,7-diphenyl fluorenyl)-1-cyclopentadienyl-1,1-dimethylmethane) zirconium dichloride;

(1-(2,7-dimesityl fluorenyl)-1-cyclopentadienyl-1,1-dimethylmethane) zirconium dichloride;

(1-(2,7-diphenyl fluorenyl)-1-cyclopentadienyl-1-phenylmethane) zirconium dichloride; and

(1-(2,7-dimesityl fluorenyl)-1-(cyclopentadienyl) cyclopentane) zirconium dichloride.
The metallocene of any of the preceding claims, wherein R" is the divalent methylene radical ―CR₂'--, wherein each R' is the same or different and selected from methyl, phenyl, and hydrogen radicals, with the proviso that at least one R' is hydrocarbyl.
The metallocene of claim 7, said metallocene being selected from

(1-(2,7-diphenyl fluorenyl)-1-cyclopentadienyl-1,1-diphenylmethane) zirconium dichloride and

(1 -(2,7-diphenyl fluorenyl)-1-cyclopentadienyl-1,1-dimethylmethane) zirconium dichloride.
A process for polymerizing an olefin, the process comprising the step of contacting said olefin under suitable polymerization conditions with a catalyst system comprising a fluorenyl-containing metallocene of the type set forth in any of claims 1 to 8 and a suitable cocatalyst such as an alkylaluminoxane.
The process of claim 9, wherein the olefin is a syndiotactic alpha-olefin having at least 3 carbon atoms.
A catalyst system for the polymerization of olefins, said catalyst system comprising a metallocene as defined in any of claims 1 to 8 and an organoaluminum cocatalyst.